Glass composition



April 1963 R. TIEDE 3,084,054

GLASS COMPOSITION Filed March 15, 1960 O 8 %U O 8 INVENTOR. RALPH L.T/EDE ,4 TTO/PNE v5 United States Patent Ofifice 3,084,054 Patented Apr.2, 1953 3,934,954 GLAS Qflh/IiQSiTil-QN Ralph L. Tiede, Nev/aria, @lnio;grant to the United States Atomic Energy Commission as the agent or" andon behalf of the United Eltates, under the provisions of 42 UEJC. 12182Fiied Mar. 15, 19%, Ser. No. 115,131 37 Qiahns. (Cl. 196-52) Thisinvention relates to glass composition-s and more specifically tocompositions suitable for fiberizing.

This application is a continuation-in-part of an application havingSerial Number 610,897, filed September 20, 1956, and now abandoned.

A great deal of work has been accomplished related to finding specificglass compositions which include uranium oxide as a necessaryingredient, which compositions are especially suited for use in chemicalprocessing and as nuclear fuels. It was earlier recognized that a glassfiber having uranium oxide as an ingredient would be desirable for theabove uses; however, the glass compositions having more than 15% uraniumoxide have now been discovered and are herein disclosed for the firsttime.

In order for the compositions to be suitable for use in the productionof fibers, they must meet an exacting set of standards. Fiberproduction, according to present-day high speed methods, requires that aglass melt be produced either from marbles, cullet or from basic rawmaterials. In either event, a rather substantial amount of molten glassis maintained for discharge in fine streams through orifices in feeders,commonly called bushings, the streams then being attenuated in any ofnumerous manners into the line fibers desired. Continuous fibers whichare pulled and wound upon a collet Winder have been produced from thecompositions of the present invention. This process is well-known to allthose skilled in the art. The invention herein relates not to processbut rather the inventive concept relates directly to the specificcompositions which provide the necessary viscositytemperaturerelationships to allow fiberization and other physical properties suchas durability and strength which have been found desirable by those whouse the fibers after they are once produced.

Glass as it is commonly known is a super-cooled liquid and is not in anequilibrium condition. As ordinary glass is heated from roomtemperature, it passes through a range of temperatures at which itsoftens, first to a relatively viscous liquid condition. Further heatingof glass above the softening range eventually brings it to a liquidus ormaximum devitrification temperature. Above the liquidus temperature theglass exists, under equilibrium conditions, as a liquid. Below suchtemperature, glass exists at equilibrium, in a crystalline state. Attemperatures just below the liquidus, devitrificatio-n occurs at a rapidrate. Glass to be fiberized must be melted and must also 'be maintained180 or so above its liquidus in order to prevent devitrification or evenpartial devitrification which might occur in the melting tank or in thevicinity of the bushing or feeder if a lower temperature weremaintained.

The range of temperatures available in commercial production forfiberization, therefore, is between the liquidus temperature of theglass being fiberized and the maximum permissible operating temperatureof the feeder. In order to be suited for the production of glass fibersby commercial techniques, glass must have a liquidus temperaturesubstantially lower than the maximum permissible operating temperatureof a feeder which is usually from about 2.500 to about 2600 F. and theglass must have a viscosity suitable for fiberization at a temperatureabove its liquidus temperature but below such maximum bushing operatingtemperature.

It is an object of this invention to provide glass compositions having ahigh proportion of uranium oxide as an essential ingredient.

It is a further object to provide compositions of the silica, soda,urania system which are fiberizable by known methods and which can,therefore, be produced economical-1y and commercially.

Further objects will be apparent from the many examples and descriptionwhich follows.

Glass compositions of the silica, soda, urania system which include fromabout 15 by weight to about 55% by weight urania are illustrated in theexamples which follow.

In the drawing FIGURE 1 represents compositions within the silica-sodiumoxide-urania system suitable for the practice of the invention.

These glass compositions have the following ranges of proportions:

S10 35-70 Na O 5-35 U 0 1 15-55 1 Preferably 19-50%.

The following are examples of specific compositions that have beenmelted and are fiberizable by known techniques.

Example I Percent SiO 34.98 A1 0 .04 N320 U 0 54.97 Fe O .02

Example II Si0 39.98 A1 0 .04 Na O 9.99 U 0 49.97 Ffizos .02

Example III Si0 34.98 A1203 .04 Na O 14.99 U 0 49.97 F2O3 .02

Example IV SiO 59.95 A1 0 .06 Na O 2 3.99 U 0 15.98 F6203 .03 Bushingoperating temperature, 21002300 F. Fiber diameter, .00008-12".

Example V Si0 62.94 A1 0 .06 Na O 19.98 U 0 16.98 F6203 Bushingoperating temperature, 2300 F. Fiber diameter, .00018.

Example VI SiO 44.97 A1 0 .05 Na O 9.99 U 0 44.97 Fe O .02

Percent 3 Example VII Percent SiO 39.98 2 3 .04 Na O 14.99 U 0 44.97F203 Example VIII SiO 34.98 A1 0 .04 Na O 19.99 U 0 44.97 F6203 .02

Example IX SiO 59.95 A1 0 .06 Na O 9.99 U 0 29.97 F8203 .03

Example X SiO 54.95 A1 0 .06 N2 0 14.99 U 0 29.97 F6203 Example XI SiO49.96 A1 0 .05 Na O 19.98 U 0 29.98 F3203 .03

Example XII SiO 44.97 A1 0 .05 Na O 24.98 U 0 29.98 F6203 .02

Bushing operating temperature, 2200 F. Fiber diameter, 0.00023".

Example XIII SiO 39.98 A1 0 .04 Na O 29.98 U 0 29.98 F3203 .02

Bushing operating temperature, 2000- F. Fiber diameter, 0.00019" ExampleXIV SiO 49.96 A1 0 .05 Na O 9.99 U 0 39.97 F2O3 -03 Example'XV SiOg44.97 A1 0 .05 Na O 14.99 U 0 39.97 F6203 .02

Example XVI Si0 39.98 A1 0 .04 Na O 19.99 U 0 39.98 Fez03 .02

Example XVII SiO 34.98 A1 0 .04 Na O 24.98 U308 F6203 .02

4 Example XVIII Percent SiO 54.95 A1 0 .06 5 Na O 9.99 U 0 34.97 Fe O.03 Bushing operating temperature, 2850 F. Fiber diameter, .00034". 10Example XIX SiO 49.96 A1 0 .05 Na O 14.99 U 0 34.97 F6203 .03

Bushing operating temperature, 2350 F.

Example XX SiO 44.97 A1 0 .05 Na O $19.99 U 0 34.97 1 6203 .02 r ExampleXXI sio 39.98 A1 0 .04 Na O 24.9.8 U 0 34.98 F6203 .02

Bushing operating temperature, 2100 F. Fiber diameter, .00015".

Example XXII SiO 51.96 30 A1 0 .05 Na O 27.98 U 0 19.98 Fe O .03

4O Bushing operating temperature, 2300 F.

Fiber diameter, .00024".

Example XXIII Si0 55.95 A1 0 .06 Na O 23.98 U 0 .19.9s

F6203 Bushing operating temperature, 2050-2300 F. Fiber diameter,00008-00016" Example XXIV SiO 59.95 A1 0 .06 Na O 19.98 U 0 19.98 Fe O.03

Bushing operating temperature, 2300 F. Fiber diameter .00013".

Example XXV 0 Slog 62.94 A1 0 .06 Na O 15.99 U 0 20.98 Fe O .03

Bushing operating temperature, 2300 F.

Fiber diameter, .00018".

Example XXVI SiO 58.95 A1 0 .06 N320 U 0 24.98 F6 0 .03

Bushing operating temperature, 2300 F. Fiber diameter, .00015".

Example XX VII Percent SiO 55.95 A1203 Na O 19.98 U 0 23.98 Fe O .03

Example XXVIII SiO 49.96 Al O .05 Na O 23.98 U 0 25.98 F203 .03

Bushing operating temperature, 2300 F. Fiber diameter, .00023".

Example XXIX SiO 49.96 A1 0 .05 Na O 9.99 U 0 34.97 F6203 .03 C210 5.00

Example XXX Si0 46.97 A1 0 .05 Na O 19.99 U 0 32.98 Fe 'O3 Bushingoperating temperature, 2300 F. Fiber diameter, .00021.

Example XXX] SiO 67.93 Al O .07 Na O 15.98 U 0 15.98 Fe O .03

Bushing operating temperature, 2200 F. Fiber diameter, 0.00010".

Example XXXH SiO 39.98 A1 0 14.99 N320 .02 U 0 30.00 F203 MgO 5.00 CaO10.00

Bushing operating temperature, 2500" F.

The fibers of this composition have good durability.

6 Fibers of this composition have good durability and resistance towater and water vapor.

Example XXXV Percent SiO 51.96 A1 0 .05 N21 O 13.99 U 0 19.98 F6203 .03R 0 13.99 ExampleXXXVl SiO 55.82 23a 2 U 0 19.94 F203 -2 A part or allof the soda can be replaced with po-tassia as illustrated in ExamplesXXXV and XXXVI. The compositions of Examples XXXII, XXXllI and XXXIVhave an addition of alumina along with the calcia and magnesia ortitania and zirconia to provide additional durability over that providedby the silica-urania-soda glass compositions. If very good durability isa prime requisite, these compositions are recommended.

Examples 1V, XXlll and XXIX set forth compositions that produced verygood fibers Which are especially suited for the purposes of thisinvention. Thus the preferred range for uran-ia appears to be from about19% to about 50% by Weight. Silica, soda and urania are consideredessential ingredients in all of these compositions. The alumina and ironoxide are present in only very small amounts as impurities in most ofthe compositions. The exceptions are Examples XXXlI, XXXllI and XXXIVwhich contain alumina in substantial portions and not as an impurityonly. Any other ingredients which are added are not believed to beessential for the purposes outlined in the objectives. Thesecompositions are melted at temperatures of from about 2600-2900 F. Thetemperature of the glass as it is fiberized is from about 2000 2850 F.The compositions disclosed have been found to be leachable by acid toproduce high temperature resistant glass fibers. Example XXXVI whenleached with acid curled up quite unexpectedly to provide a novelproduct.

Modifications and variations Within the scope of the appended claims areintended to be included.

I claim:

1. A glass composition consisting essentially of from 35-70% by WeightSiO from 5-35% by weight Na O, and from 1660% by Weight U 0 2. Glasscomposition fiberizable by conventional processes comprising by weight,34.98% SiO 0.04% A1 0 9.99% Na o, 54.97% U 0 and 0.02% Fe O 3. Glasscomposition fiberizable by conventional processes comprising by weight,39.98% SiO 0.04% A1 0 N320, U308, and FEzO-g.

4. Glass composition fiberizable by conventional processes comprising byWeight, 34.98% SiO 0.04% A1 0 14.99% Na O, 49.97% U 0 and 0.02% Fe O 5.Glass composition fiberizable by conventional processes comprising byWeight, 59.95% SiO 0.06% A1 0 23.99% Na O, 15.98% U 0 and 0.03% Fe O 6.Glass composition fiberizable by conventional processes comprising byWeight, 62.94% SiO 0.06% A1 0 19.98% Na O, 16.98% U 0 and 0.03% Fe O 7.Glass composition fiberizable by conventional processes comprising byweight, 44.97% SiO 0.05% A1 0 9.99% Na O, 44.97% U 0 and 0.02% Fe O 8.Glass composition fiberizable by conventional processes comprising byWeight, 39.98% SiO 0.04% A1 0 14.99% Na O, 44.97% U 0 and 0.02% Fe 0 9.Glass composition fiberizable by conventional proc esses comprising byWeight, 34.98% SiO 0.04% A1 0 19.99% Na O, 44.97% U 0 and 0.02% Fe O 710. Glass composition fiberizable by conventional processes comprisingby weight, 59.95% S10 0.06% A1 9.99% Na O, 29.97% U 0 and 0.03% Fe O 11.Glass composition fiberizable by conventional processes comprising byweight, 54.95% SiO 0.06% A1 0 14.99% Na O, 29.97% U 0 and 0.03% Fe O 12.Glass composition fiberizable by conventional processes comprising byweight, 49.96% SiO 0.05% A1 0 19.98% Na O, 29.98% U 0 and 0.03% Fe O 13.Glass composition fiberizable by conventional processes comprising byweight, 44.97% Sio 0.05% A1203, N320, U308, and F0203. 14. Glasscomposition fiberizable by conventional processes comprising by weight,39.98% SiO 0.04% A1203, N320, U303, and F6203. 15. Glass compositionfiberizable by conventional processes comprising by weight, 49.96% SiO0.05% A1203, N320, U308, and F0203. 16. Glass composition fiberizable byconventional processes comprising by weight, 44.97% SiO- 0.05% A1203,14.99% Na20 39.97% U308, and 0.02% Fe203. 17. Glass compositionfiberizable by conventional processes comprising by weight, 39.98% SiO0.04% A1203, 14.99% NazO, 39.98% U308, and 0.02% F6203. 18. Glasscomposition fiberizable by conventional processes comprising by weight,34.98% SiO 0.04% A1203, N320, U308, and F0203. 19. Glass compositionfiberizable by conventional processes comprising by weight, 54.95% SiO0.06% A1 0 9.99% N2 0, 34.97% U 0 and 0.03% Fe O 20. Glass compositionfiberizable by conventional processes comprising by weight, 49.96% SiO0.05% A1 0 14.99% N320, 34.97% U 0 and 0.03% Fe O 21. Glass compositionfiberizable by conventional processes comprising by weight, 44.97% SiO0.05% A1 0 19.99% Na O, 34.97% U 0 and 0.02% Fe O 22. Glass compositionfiberizable by conventional processes comprising by weight, 39.98% SiO0.04% A1 0 24.98% Na -O, 34.98% U 0 and 0.02% Fe O 23. Glass compositionfiberizable by conventional processes comprising by weight, 51.96% SiO0.05% A1 0 27.98% Na O, 19.98% U 0 and 0.03% Fe O 24. Glass compositionfiberizable by conventional processes comprising by weight, 55.95% SiO0.06% A1 0 23.98% Na O, 19.98%'U O and 0.03% Fe O 25. Glass compositionfiberizable by conventional processes comprising by weight, 59.95% SiO0.06% A1 0 19.98% Na O, 19.98% U O and 0.03% Fe O 26. Glass compositionfiberizable by conventional processes comprising by-weight, 62.94% S100.06% A1 0 15.99% Na O, 20.98% U 0 and 0.03% -Fe O 27. Glass compositionfiberizable by conventional processes comprising by weight, 58.95% SiO.006% A1203, N320, U308, and F0203.

28. Glass composition fiberizable by conventional processes comprisingby weight, 55.95% SiO 0.06% A1 0 19.98% Na O, 23.98% U 0 and 0.03% Fe O29. Glass composition fiberizable by conventional processes comprisingby weight, 49.96% SiO 0.05% A1 0 23.98% Na O, 25.98% U 0 and 0.03%F3203.

30. Glass composition fiberizable by conventional processes comprisingby weight, 49.96% SiO 0.05% A1203, N320, U308, F0203, and 5.00% CaO.

31. Glass composition fiberizable by conventional processes comprisingby weight, 46.97% SiO 0.05% A1203, N320, U308, and F6203.

32. Glass composition fiberizable by conventional processes comprisingby weight, 67.93% SiO 0.07% A1203, N320, U308, and F6203.

33. Glass composition fiberizable by conventional processes comprisingby weight, 39.98% SiO 14.99% A1 0 0.02%Na O, 30.00% U 0 0.02% Fe O 5.00%MgO, and 10.00% CaO.

34. Glass composition fiberizable by conventional processes comprisingby weight, 39.98% SiO 14.99% A1 0 0.02% Na O, 29.99% U 0 0.02% Fe O7.50% MgO, and 7.50% CaO.

35. Glass composition fiberizable by conventional processescompr-ising'by weight, 38.86% SiO 7.75% A1 0 15.51% Na O', 22.34% U 00.02% Fe O 11.63% TiO and 3.89% ZrO 36. Glass composition fiberizable byconventional processes comprising by weight, 51.96% SiO 0.05% A1 013.99% Na O, 19.98% U 0 0.03% F0 0 and 13.99% K 0.

37. Glass composition fiberizable by conventional processes comprisingby weight, 55.82% SiO 0.23% A1 0 23.92% K 0, 19.94% U 0 and 0.09% Fe O12, page 45,

1. A GLASS COMPOSITION ESSENTIALLY OF FROM 35-70% BY WEIGHT SIO2, FROM5-35% BY WEIGHT NA2O,